Visible light active biomass derived photoinitiators

This is the national phase application of international application PCT/US2021/032893, filed under the authority of the Patent Cooperation Treaty on May 18, 2021, published; which claims priority to U.S. Provisional Application No. 63/026,970 filed under 35 U.S.C. § 111(b) on May 19, 2020. The entire disclosure of each of the aforementioned applications is incorporated herein by reference in its entirety for all purposes.

This invention was made with no government support. The government has no rights in this invention.

Photoinitiators are widely used for various applications that involves UV curing. These include automobile parts manufacturing, automobile parts, 3D printing, contact lenses, resin curing, silicones, epoxies, dental composites, aircraft parts, and composites. Most conventional photoinitiators require UV light. There is a need in the art for new and improved photoinitiators have features that will be compatible to existing formulations but will have the ability to work under visible light conditions.

Provided herein is a composition comprising Formula Bz-1:

where dashed lines indicate optional bonds; X=O, S, NH, Ge, NC(O)—O—R, N—O—C(O)R, or NO—R, wherein Ris alkyl, aryl, or heteroaryl; A or B is a ring derived from biomass; and substituents Rto Rand Rto Rcan be any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes.

In certain embodiments, the composition comprises Formula A:

where units A and B represent an alkyl chain, a carbocycle, a heterocyclic moiety, or a combination of C—C or C-heteroatom bonds, optionally substituted with one or more electron withdrawing (e.g., alkoxy) or electron donating substituents (e.g., halogens). X can feature an alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or hetero-atom attached to a carbocycle or a heterocycle. In certain embodiments, at least one of the units A, B, or X is derived from bio-mass.

In certain embodiments, the composition comprises bis-(dimethoxy)-benzoin 1a:

In certain embodiments, the composition comprises para-chlorobenzyl-(dimethoxy)-benzoin 1b:

In certain embodiments, the composition comprises para-cyanobenzyl-(dimethoxy)-benzoin 1c:

In certain embodiments, the composition comprises para-trifluoromethylbenzyl-(dimethoxy)-benzoin 1d:

In certain embodiments, the composition comprises para-chlorobenzoyl-(dimethoxy)-benzoin 1e:

In certain embodiments, the composition comprises para-thiomethylbenzyl-(dimethoxy)-benzoin 1f:

In certain embodiments, the composition comprises para-thiomethylbenzoyl-(dimethoxy)-benzoin 1g:

In certain embodiments, the composition comprises compound para-fluorobenzyl-(dimethoxy)-benzoin 1i:

In certain embodiments, the composition comprises compound para-fluorolbenzoyl-(dimethoxy)-benzoin 1j:

Further provided is a composition comprising Formula Bz-2 or Formula Bz-3:

wherein dashed lines indicate optional bonds; X=O, S, NH, Ge, NC(O)—O—R, N—O—C(O)R, or NO—R, wherein Ris alkyl, aryl, or heteroaryl; A or B is a ring derived from biomass; substituents Rto Rand Rto Rcan be any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitrites, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes; and the polymer unit is vinyl, stryl, acryl, or cyclic monomers selected from lactones (cyclic esters), epoxides, lactides, lactams, silicon-containing cyclic monomers, and cyclic carbonates.

In certain embodiments, the composition comprises Bz-2a:

where Ris alkyl, aryl, or heteroaryl.

In particular embodiments, the composition comprises Bz-2a-I:

wherein m and n are each integers.

In certain embodiments, the composition comprises compound Bz-2b:

In certain embodiments, the composition comprises Bz-2b-I:

wherein m and n are each integers.

In certain embodiments, the composition comprises compound Bz-2b:

In certain embodiments, the composition comprises compound Bz-2d:

In certain embodiments, the composition comprises Bz-3a:

wherein Ris alkyl, aryl, or heteroaryl.

In particular embodiments, the composition comprises Bz-3a-I:

wherein m and n are each integers.

In certain embodiments, the composition comprises compound Bz-3b:

In certain embodiments, the composition comprises compound Bz-3c:

In certain embodiments, the composition comprises compound Bz-3d:

Further provided is a composition comprising Formula Bz-4 or Formula Bz-5: